Mesoporous catalyst support, a catalyst system, and method of making and using same for olefin polymerization

ABSTRACT

This invention relates to a catalyst system comprising a catalyst and a support comprising a non-layered inorganic porous crystalline phase material, wherein the support comprises a hexagonal arrangement of uniformly-sized pores having an average pore diameter greater than or equal to about 13 Å, an X-ray diffraction pattern having a calculated d 100  value of greater than or equal to about 18 Å, an adsorption capacity of greater than or equal to about 15 grams benzene per 100 grams support at 50 torr and at 25° C., and a pore wall thickness of less then or equal to about 25 Å.

PRIORITY CLAIM

This invention is a divisional of U.S. Ser. No. 10/758,824, filed Jan.16, 2004 now U.S. Pat. No. 7,151,073.

FIELD OF THE INVENTION

This invention relates to a catalyst support, a catalyst system, and amethod of making and using the catalyst system as well as the polymersand other materials produced thereby.

BACKGROUND OF THE INVENTION

The availability of polyethylene and other polymers derived frompolymerization of olefins have revolutionized modem society. Suchmaterials are responsible for innovations, which touch and concernnearly every aspect of modem day life. Polymerization catalysts used inobtaining these materials thus offer opportunities for providing newprocesses and products to the markets. In particular, supported olefinpolymerization catalyst systems are of great interest in makingpolymeric products available.

Metal containing catalysts may be used in producing polyolefins fromalpha-olefins such as ethylene. Polyolefins may be produced bycontacting olefins under polymerization conditions with “Ziegler” typecatalyst, which may have a Group 4 or 5 transition metal component. Aco-catalyst may also be present; see for example U.S. Pat. Nos.4,224,185, 4,220,555, 4,143,223, 3,623,846, and British Pat. No.1,139,450 directed to a co-catalyst comprising titanium, which may beactivated with an organometallic compound.

Chromium compounds and complexes may also be used as catalysts for thepolymerization of olefins. U.S. Pat. Nos. 3,324,095, 3,324,101,3,642,749, and 3,704,287 are directed to a catalyst, which includessilyl chromate and polyalicyclic chromate esters. U.S. Pat. Nos.3,704,287, 3,474,080, and 3,985,676 are directed tophosphorus-containing chromate esters which may also be used in olefinpolymerization catalysts. U.S. Pat. No. 4,359,562 is directed to aprocess of ethylene polymerization using a supportedchromium-hydrocarbon complex, and WO2000/61645 is directed to apolymerization catalyst that includes chromium in combination with anorganoaluminum material, and an organomagnesium material.

Other chromium catalysts may include: U.S. Pat. Nos. 3,324,101,3,642,749, 3,704,287, 3,806,500, and 4,467,080, which are directed tochromium compound catalysts in coordination catalyst systems; U.S. Pat.No. 6,300,272 directed to chromium catalyst on a silica support; U.S.Pat. No. 6,245,869 directed to a chromium-based catalyst having a silicaand titania support along with a co-catalyst of an aluminum or zincalkyl; and U.S. Pat. No. 6,096,679 directed to a chromium-based catalystfor the production of polyethylene using a catalyst support of silica,silica-titania, or silica-zirconia.

Catalysts may also be associated with a support. See for example U.S.Pat. Nos. 2,852,721 and 2,951,816, directed to the use of CrO₃ supportedon an inorganic material that may include silica, alumina orcombinations of silica and alumina, and which may be activated byheating in a reducing atmosphere. Combinations of different catalysts ona support may also be used to produce polyolefins, examples include:U.S. Pat. No. 3,882,096 directed to a catalyst and method of preparingultra high molecular weight polyolefins using chromium oxide on asupport in combination with an alkyl ester of titanium; U.S. Pat. No.3,622,522 directed to an alkoxide of gallium or tin added to supportedchromium oxide prior to heat activation; U.S. Pat. No. 3,715,321directed to adding a compound of a Group 2 or Group 3 metal to supportedchromium oxide prior to heat treatment; U.S. Pat. No. 3,780,011 directedto adding alkyl esters of titanium, vanadium or boron; U.S. Pat. No.3,484,428 directed to adding alkyl boranes to a supported catalyst; andU.S. Pat. No. 5,189,000 directed to using organometallic compound ofaluminum with a titanium, vanadium, or chromium catalyst.

Aluminosilicates and other siliceous materials may be used as supportsfor olefin polymerization catalysts. U.S. Pat. Nos. 5,057,296 and5,200,058 are directed to a catalyst comprising an active form of afunctionalized inorganic, porous, non-layered crystalline phase havinguniformly sized pores of at least about 13 Å, and a Group 6 metal. U.S.Pat. Nos. 5,105,051 and 5,270,273 are directed to oligomerizing alphaolefins to produce hydrocarbon oligomers useful as lubricants andlubricant additives using a catalyst comprising a supported reducedGroup 6 metal, preferably chromium, in the form of its oxide on amesoporous, inorganic, crystalline solid having a specific pore geometrydescribed as a uniform hexagonal honeycomb microstructure, with uniformpores having a cell diameter greater than 13 Å. InternationalApplication WO2002/40551, and EP 827,969 A2 are directed to usingmesoporous supports having pore diameters of from 2 to 10 nanometers.

An olefin polymerization process may comprise contacting a catalyst withthe olefin at constant temperature and pressure. Upon this contacthowever, a lag time referred to herein as an induction time may thenensue prior to an appreciable commencement of the polymerizationprocess. This induction time may be monitored by the consumption of theolefin feed stock flowing into the constant pressure reactor.Accordingly, it is beneficial to utilize a catalyst system, whichprovides a polymer having the desired properties, at the desired rate ofconversion, which also provides for a relatively low induction time.However, chromium based catalysts systems may be characterized as havingrelatively long induction times with relatively low rates of conversion.Accordingly, there remains a need for supported chromium based catalystshaving relatively short induction times that provide for relatively highcatalytic activities under polymerization conditions, and which producepolymers having desired attributes which may include a particular bulkdensity, molecular weight distribution, and/or the like.

Other References of Interest Include:

-   1. U.S. Pat. No. 5,220,101; Sorption separation over modified    synthetic mesoporous crystalline material-   2. U.S. Pat. No. 5,171,915; Alkylaromatic lubricants from    alpha-olefin dimer-   3. U.S. Pat. No. 5,146,021; Enhancing compositions and Newtonian    lube blends-   4. U.S. Pat. No. 5,145,816; Method for functionalizing synthetic    mesoporous crystalline material-   5. U.S. Pat. No. 5,132,477; Process for producing alkylaromatic    lubricant fluids-   6. U.S. Pat. No. 5,105,051; Production of olefin oligomer lubricants-   7. U.S. Pat. No. 5,105,039; Process for producing lubricant fluids    of improved stability-   8. U.S. Pat. No. 5,087,782; Dehydrocyclization of polyalpha-olefin    lubricants-   9. U.S. Pat. No. 5,019,670; Process for producing alkylaromatic    lubricant fluids-   10. U.S. Pat. No. 5,015,795; Novel synthetic lube composition and    process-   11. U.S. Pat. No. 4,996,384; Regeneration of reduced metal oxide    oligomerization catalyst-   12. U.S. Pat. No. 4,990,718; Aromatic alkylation with alpha-olefin    dimer-   13. U.S. Pat. No. 4,967,030; Hydrocracking high viscosity synthetic    lubricant-   14. U.S. Pat. No. 4,926,004; Regeneration of reduced supported    chromium oxide catalyst for alpha-olefin oligomerization-   15. U.S. Pat. No. 4,914,254; Fixed bed process for high viscosity    index lubricant-   16. U.S. Pat. No. 4,711,710; Process for making improved lubricating    oils from heavy feedstock

SUMMARY OF THE INVENTION

This invention relates to a catalyst system comprising a catalyst and asupport comprising a non-layered inorganic porous crystalline phasematerial, wherein the support comprises a hexagonal arrangement ofuniformly-sized pores having an average pore diameter greater than orequal to about 13 Å, an X-ray diffraction pattern having a calculatedd₁₀₀ value of greater than or equal to about 18 Å, an adsorptioncapacity of greater than or equal to about 15 grams benzene per 100grams support at 50 torr and at 25° C., and a pore wall thickness ofless then or equal to about 25 Å.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a new class of catalytic supports useful tooligomerize and/or polymerize an unsaturated monomer. This inventionfurther relates to a catalyst system comprising the catalytic support, amethod of making the catalyst system, and a method of using the catalystsystem. This invention also relates to the polymers produced therefrom.

For the purposes of this invention and the claims thereto, when apolymer is referred to as comprising an olefin, the olefin present inthe polymer is the polymerized form of the olefin. A catalyticallyactive material may be interchangeably referred to as a catalyticmaterial, or a catalyst. A catalyst system comprises a catalyst and asupport. A reactor is any container(s) in which a chemical reactionoccurs. In addition, the numbering scheme for the Periodic Table Groupsused herein is the “New Notation” as described in CHEMICAL ANDENGINEERING NEWS, 63(5), 27 (1985). Temperatures are listed in degreesCelsius (° C.) unless otherwise noted.

A porous material is a material that adsorbs at least about 1 gram ofnitrogen, n-hexane, cyclohexane, or benzene per 100 grams of thematerial. A porous material or particle having pores in the mesoporousrange comprises pores with a diameter at the surface of the particle ofgreater than or equal to about 20 angstroms (Å) and less than or equalto about 500 Å. Pore size is the a maximum perpendicular cross-sectionalpore dimension of the material. Pore wall thickness it the averagethickness between pores as measured perpendicular to the pore wallsurface. For purposes of this invention, pore wall thickness isdetermined by multiplying the d₁₀₀ peak value in angstroms by 1.155 andthen subtracting the average pore diameter in angstroms (as determinedby the BJH adsorption plot of nitrogen adsorption). In the event thatthe d₁₀₀ is obscured or otherwise unavailable, then the pore wallthickness is determined by multiplying the d₂₀₀ peak value in angstromsby 2.31 and then subtracting the average pore diameter in angstroms (asdetermined by the BJH adsorption plot of nitrogen adsorption). In theevent that the d₁₀₀ and d₂₀₀ peaks are obscured or otherwiseunavailable, then the pore wall thickness is determined by multiplyingthe d₃₀₀ peak value in angstroms by 3.465 and then subtracting theaverage pore diameter in angstroms (as determined by the BJH adsorptionplot of nitrogen adsorption).

Further, for purposes of this invention, Me is methyl, Ph is phenyl, Etis ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu isbutyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiarybutyl, TMS is trimethylsilyl, a per fluoro radical is an organic radicalhaving one or more available hydrogen atoms substituted with fluorineatoms, EO is an ethylene oxide moiety (i.e., —CH₂CH₂—O—), and PO is apropylene oxide moiety (i.e., —CH₂CH3CH₂—O—).

Catalyst Support

The catalyst support, also referred to as a catalytic support or simplyas a support, is preferably a non-layered inorganic porous crystallinephase material, which comprises a hexagonal arrangement of uniformlysized pores. The crystalline material suitable for use herein may becharacterized by its structure, including the size of the pore windows,and by sorption capacity.

The preferred support material is an inorganic material comprising acrystalline phase material. The crystalline phase material has acomposition expressed as follows:M_(n/q)(W_(a)X_(b)Y_(c)Z_(d)O_(h))where M is one or more ions, such as ammonium, Group 1, 2 and 17 ions,preferably hydrogen, sodium and/or fluoride ions;

n is the charge of the composition excluding M expressed as oxides;

q is the weighted molar average valence of M;

n/q is the number of moles or mole fraction of M;

W is one or more divalent elements, such as a divalent first rowtransition metal, e.g. manganese, cobalt, iron, and/or magnesium (forpurposes of this invention the symbol W is not meant to indicate theelement tungsten);

X is one or more trivalent elements, such as aluminum, boron, ironand/or gallium, with aluminum preferred;

Y is one or more tetravalent elements such as silicon and/or germanium,with silicon preferred;

Z is one or more pentavalent elements, such as phosphorus;

O is oxygen;

a, b, c, and d are mole fractions of W, X, Y and Z, respectively;

h is a number of from 1 to 2.5; and

(a+b+c+d)=1.

A preferred embodiment of the above support is when (a+b+c) is greaterthan d, and h=2. A further embodiment is when a=0, d=0, and h=2, whichmay include an aluminosilicate.

The preferred aluminosilicates have a silica-to-alumina molar ratio ofabout 5:1 to about 1000:1. Preferably, the support is an aluminosilicatecharacterized as having an alumina weight percent (Al₂O₃ wt %) of about0.1 to about 20 Al₂O₃ wt %, based on the total weight of the support.Within this range, an alumina weight percent of less than or equal toabout 15 can be employed, with less than or equal to about 10 Al₂O₃ wt %more preferred. Also preferred within this range is weight percent ofgreater than or equal to about 1, with greater than or equal to about 4Al₂O₃ wt % more preferred. In a preferred embodiment, a and d are 0,h=2, X comprises aluminum, and Y comprises silicon.

Prior to calcination, (in the as-synthesized form), preferred supportmaterial preferably has a composition, on an anhydrous basis, expressedempirically as follows:rRM_(n/q)(W_(a)X_(b)Y_(c)Z_(d)O_(h));wherein R is the total organic material not included in M as an ion, ris the coefficient for R, i.e. the number of moles or mole fraction ofR, where W, X, Y, Z, O, n, q, a, b, c, d, and h are as defined above.The M and R components are associated with the material as a result oftheir presence during crystallization, and are easily removed or, in thecase of M, replaced by post-crystallization methods hereinafter moreparticularly described. To the extent desired, the original M cations,e.g. sodium or chloride ions of the as-synthesized material can bereplaced at least in part, by ion exchange with other ions. Preferredreplacing ions include metal ions, hydrogen ions, hydrogen precursorsincluding ammonium ions, and mixtures of ions.

Preferably, the support material is crystalline in that it provides adiffraction pattern with at least one peak by X-ray, electron or neutrondiffraction, following calcination. The catalytic support preferablyyields an X-ray diffraction pattern with a few distinct maxima in theextreme low angle region. The positions of these peaks preferablyapproximately fit the positions of the hkO reflections from a hexagonallattice. The X-ray diffraction pattern, however, may not always be asufficient indicator of the presence of these materials, as the degreeof regularity in the microstructure and the extent of repetition of thestructure within individual particles affect the number of peaks thatwill be observed. Indeed, preparations with only one distinct peak inthe low angle region of the X-ray diffraction pattern have been found tocomprise the present support material.

In its calcined form, the non-layered inorganic porous crystalline phasematerial may be characterized by an X-ray diffraction pattern with atleast one peak at a position greater than about 18 Angstrom Units (Å)d-spacing (4.909 degrees two-theta for Cu K-alpha radiation). Moreparticularly, the calcined crystalline material of the invention may becharacterized by an X-ray diffraction pattern with at least two peaks atpositions greater than about 10 Å d-spacing (8.842-degrees two-theta forCu K-alpha radiation), at least one of which is at a position greaterthan about 18 Å d-spacing, and no peaks at positions less than about 10Å d-spacing with relative intensity greater than about 20% of thestrongest peak. Still more particularly, the X-ray diffraction patternof the calcined support material will have no peaks at positions lessthan about 10 Å d-spacing with relative intensity greater than about 10%of the strongest peak.

The calcined non-layered inorganic porous crystalline phase material maybe characterized as having a pore size greater than or equal to about 13Å as measured by physio-sorption measurements more particularly setforth herein.

The support may also be characterized based on sorption characteristics.Preferably, the non-layered inorganic porous crystalline phase materialhas an equilibrium benzene adsorption capacity of greater than about 15grams benzene/100 grams support at 50 torr and 25° C., based onanhydrous crystal material having been treated to insure no poreblockage by incidental contaminants is present. Accordingly, thesorption tests are conducted on the crystalline material phase havingany pore blockage contaminants and water removed. Water may be removedby dehydration techniques, e.g. thermal treatment. Pore blockinginorganic amorphous materials, e.g. silica, and organics may be removedby contact with acid or base or other chemical agents such that thedetrital material will be removed without detrimental effect on thenon-layered inorganic porous crystalline phase material.

Preferably, the equilibrium benzene adsorption capacity is determined bycontacting the anhydrous material of the invention, after oxidativecalcination at 450° C.-700° C. for at least one hour, and othertreatment, if necessary, to remove any pore blocking contaminants, at25° C. and 50 torr benzene until equilibrium is reached. The weight ofbenzene sorbed (i.e., adsorbed) is then determined.

The equilibrium benzene adsorption capacity at 50 torr and 25° C., basedon anhydrous crystal material having been treated to insure no poreblockage by incidental contaminants is present, is preferably greaterthan or equal to about 20 grams benzene/100 grams support, morepreferably greater than or equal to about 25 grams benzene/100 gramssupport.

The equilibrium cyclohexane adsorption capacity at 50 torr and 25° C.,based on anhydrous crystal material having been treated to insure nopore blockage by incidental contaminants is present is preferablygreater than or equal to about 15 grams cyclohexane/100 grams support,more preferably greater than or equal to about 20 grams cyclohexane/100grams support, still more preferably greater than or equal to about 25grams cyclohexane/100 grams support.

The non-layered inorganic porous crystalline phase material may besynthesized with Bronsted acid active sites by incorporating atetrahedrally coordinated trivalent element, such as Al, Ga, B, or Fe,within the silicate framework. Aluminosilicate materials of this typemay be thermally and chemically stable, which are properties favored foracid catalysis. In addition, the mesoporous structures of the supportmay be utilized by employing highly siliceous materials or crystallinemetallosilicate having one or more tetrahedral species having varyingdegrees of acidity. In addition to aluminosilicates, gallosilicate,ferrosilicate and borosilicate materials may also be employed.

The non-layered inorganic porous crystalline phase material can beprepared from a reaction mixture containing sources of, for example,alkali or alkaline earth metal (M), e.g. sodium or potassium cation, oneor a combination of oxides comprising: a divalent element W, e.g.cobalt; a trivalent element X, e.g. aluminum; a tetravalent element Y,e.g. silicon; a pentavalent element Z, e.g. phosphorus; an organic (R)directing agent or agents; and a solvent or solvent mixture with waterbeing preferred. The reaction mixture preferably has a composition, interms of mole ratios of oxides, within the following ranges:

Preferred Range More Preferred Range Greater than or equal to Greaterthan or equal to about     to about     (Mole about     to about    (Mole Reactants ratio of oxides) ratio of oxides) X₂O₃/YO₂   0 to 0.050.001 to 0.05  X₂O₃/(YO₂ + Z₂O₅) 0.1 to 100  0.1 to 20  X₂O₃/(YO₂ + WO +Z₂O₅) 0.1 to 100  0.1 to 20  Solvent/YO₂  1 to 1500   5 to 1000 OH—/YO₂0.01 to 10   0.05 to 5   (M_(2/e)O + R_(2/f)O)/(YO₂ + WO + Z₂O₅ + X₂O₃)0.01 to 20   0.05 to 5   M_(2/e)O/(YO₂ + WO + Z₂O₅ + X₂O₃) 0 to 10 0.005to 5   wherein e and f are the weighted average valences of M and R,respectively.

In a preferred embodiment X is aluminum and Y is silicon in the abovetable.

When no Z and/or W oxides are added to the reaction mixture, the pH ispreferably maintained at from about 10 to about 14. When Z and/or Woxides are present in the reaction mixture, the pH may vary betweenabout 1 and 14 for crystallization of the non-layered inorganic porouscrystalline phase material.

The crystalline support material can be prepared by one of severalmethods. One preferred method may include a reaction mixture having anX₂O₃/YO₂ mole ratio of from 0 to about 0.5, and an Al₂O₃/SiO₂ mole ratioof from 0 to 0.01, a crystallization temperature of from about 25° C. toabout 250° C., preferably from about 50° C. to about 175° C., and anorganic directing agent, or preferably a combination of an organicdirecting agent with an additional organic directing agent. Thispreferred method comprises preparing a reaction mixture containingsources of, for example, alkali or alkaline earth metal (M), e.g. sodiumor potassium cation, one or a combination of oxides comprising: adivalent element W, e.g. cobalt; a trivalent element X, e.g. aluminum; atetravalent element Y, e.g. silicon; a pentavalent element Z, e.g.phosphorus; an organic (R) directing agent or agents; and a solvent orsolvent mixture such as, for example, C₁-C₆ alcohols, C₁-C₆ diols and/orwater, with water being preferred. The reaction mixture preferably has acomposition, in terms of mole ratios of oxides, within the followingranges:

Preferred Range More Preferred Range Greater than or equal to Greaterthan or equal to about     to about     (Mole about     to about    (Mole Reactants ratio of oxides) ratio of oxides) X₂O₃/YO₂   0 to 0.050.001 to 0.05  Al₂O₃/SiO₂   0 to 0.01 0.001 to 0.01  X₂O₃/(YO₂ + Z₂O₅)0.1 to 100  0.1 to 20  X₂O₃/(YO₂ + WO + Z₂O₅) 0.1 to 100  0.1 to 20 Solvent/(YO₂ + WO + Z₂O₅ + X₂O₃)  1 to 1500   5 to 1000 OH—/YO₂ 0 to 100.05 to 5   (M_(2/e)O + R_(2/f)O)/(YO₂ + WO + Z₂O₅ + X₂O₃) 0.01 to 20  0.05 to 5   M_(2/e)O/(YO₂ + WO + Z₂O₅ + X₂O₃) 0 to 10 0.005 to 5   R_(2/f)O/(YO₂ + WO + Z₂O₅ + X₂O₃) 0.01 to 2.0  0.03 to 1.0 where e and f are the weighted average valences of M and R,respectively. In this method, when no Z and/or W oxides are added to thereaction mixture, the pH is preferably maintained at from about 9 toabout 14. In a preferred embodiment X is aluminum and Y is silicon inthe above table.

A second method for synthesis of the crystalline material involves areaction mixture having an X₂O₃/YO₂ mole ratio of from about 0 to about0.5, a crystallization temperature of from about 25° C. to about 250°C., preferably from about 50° C. to about 175° C., and preferably twoseparate organic directing agents, i.e. the organic and additionalorganic directing agents. This preferred method comprises preparing areaction mixture containing sources of, for example, alkali or alkalineearth metal (M), e.g. sodium or potassium cation, one or a combinationof oxides comprising: a divalent element W, e.g. cobalt; a trivalentelement X, e.g. aluminum; a tetravalent element Y, e.g. silicon; apentavalent element Z, e.g. phosphorus; an organic (R) directing agentand an additional directing agents; and a solvent or solvent mixturesuch as, for example, C₁-C₆ alcohols, C₁-C₆ diols and/or water, withwater being preferred. The reaction mixture preferably has acomposition, in terms of mole ratios of oxides, within the followingranges:

Preferred Range More Preferred Range Greater than or equal to Greaterthan or equal to about     to about     (Mole about     to about    (Mole Reactants ratio of oxides) ratio of oxides) X₂O₃/YO₂   0 to 0.050.001 to 0.05  X₂O₃(YO₂ + Z₂O₅) 0.1 to 100  0.1 to 20  X₂O₃/(YO₂ + WO +Z₂O₅) 0.1 to 100  0.1 to 20  Solvent/(YO₂ + WO + Z₂O₅ + X₂O₃)  1 to 1500  5 to 1000 OH—/YO₂ 0 to 10 0.05 to 5   (M_(2/e)O + R_(2/f)O)/(YO₂ +WO + Z₂O₅ + X₂O₃) 0.01 to 20   0.05 to 5   M_(2/e)O/(YO₂ + WO + Z₂O₅ +X₂O₃) 0 to 10 0.005 to 5    R_(2/f)O/(YO₂ + WO + Z₂O₅ + X₂O₃) 0.1 to2.0  0.12 to 1.0 where e and f are the weighted average valences of M and R,respectively. In a preferred embodiment X is aluminum and Y is siliconin the above table.

In this second method, when no Z and/or W oxides are added to thereaction mixture, the pH is preferably maintained at from about 9 toabout 14.

A third method for synthesis of the crystalline material is where Xcomprises aluminum and Y comprises silicon, the crystallizationtemperature is preferably from about 25° C. to about 175° C., preferablyfrom about 50° C. to about 150° C., and an organic directing agent,preferably a combination of an organic directing agent plus anadditional organic agent is used. This method comprises preparing areaction mixture containing sources of, for example, alkali or alkalineearth metal (M), e.g. sodium or potassium cation if desired, one or moresources of aluminum and/or silicon, an organic (R) directing agent, anda solvent or solvent mixture such as, for example C₁-C₆ alcohols, C₁-C₆diols and/or water, with water being preferred. The reaction mixture hasa composition, in terms of mole ratios of oxides, within the followingranges:

Preferred Range More Preferred Range Greater than or equal to Greaterthan or equal to about     to about     (Mole about     to about    (Mole Reactants ratio of oxides) ratio of oxides) Al₂O₃/SiO₂   0 to 0.50.001 to 0.05  Solvent/SiO₂   1 to 1500   5 to 1000 OH—/SiO₂  0 to 100.05 to 5   (M_(2/e)O + R_(w/f)O)/(SiO₂ + Al₂O₃) 0.01 to 20   0.05 to5   M_(2/e)O/(SiO₂ + Al₂O₃) 0 to 5 0.005 to 3    R_(w/f)O/(SiO₂ + Al₂O₃)0.01 to 2.0  0.03 to 1.0 where e and f are the weighted average valences of M and R,respectively. The pH is preferably maintained at from about 9 to about14.Methods 1-3 Involves the Following Steps:

-   (1) Mix the organic (R) directing agent with the solvent or solvent    mixture such that the mole ratio of solvent/R_(2/f)O is within the    range of from about 50 to about 800, preferably from about 50    to 500. This mixture constitutes the “primary template” for the    synthesis method.-   (2) To the primary template mixture of step (1) add the sources of    oxides, e.g. silica and/or alumina such that the ratio of    R_(2/f)O/(SiO₂+Al₂O₃) is within the range of from about 0.01 to    about 2.0.-   (3) Agitate the mixture resulting from step (2) at a temperature of    from about 20° C. to about 40° C., preferably for about 5 minutes to    about 3 hours.-   (4) Allow the mixture to stand with or without agitation, preferably    at a temperature of from about 20° C. to about 100° C., and    preferably for about 10 minutes to about 24 hours.-   (5) Crystallize the product from step (4) at a temperature of about    50° C. to about 175° C., preferably for about 1 hour to about 72    hours. Crystallization temperatures higher in the given ranges are    more preferred.

A fourth method for the synthesis of the non-layered inorganic porouscrystalline phase material involves the reaction mixture used for methodthree, and also includes the following specific procedure usingtetraethylorthosilicate as the source of silicon oxide:

-   (1) Mix the organic (R) directing agent with the solvent or solvent    mixture such that the mole ratio of solvent/R_(2/f)O is within the    range of from about 50 to about 800, preferably from about 50    to 500. This mixture constitutes the “primary template” for the    synthesis method.-   (2) Mix the primary template mixture of step (1) with    tetraethylorthosilicate and a source of aluminum oxide, if desired,    such that the R_(2/f)O/SiO₂ mole ratio is in the range of from about    0.5 to about 2.0.-   (3) Agitate the mixture resulting from step (2) for about 10 minutes    to about 6 hours, preferably about 30 minutes to about 2 hours, at a    temperature of about 0° C. to about 25° C., and a pH of less    than 12. This step permits hydrolysis/polymerization to take place    and the resultant mixture may appear cloudy.-   (4) Crystallize the product from step (3) at a temperature of about    25° C. to about 150° C., preferably about 95° C. to about 110° C.,    for about 4 to about 72 hours, preferably about 16 to about 48    hours. Crystallization of the support can be carried out under    either static or agitated, e.g. stirred, conditions in a suitable    reactor vessel, such as for example, polypropylene jars or Teflon    lined or stainless steel autoclaves. The range of temperatures for    crystallization is preferably about 50° C. to about 250° C. for a    time sufficient for crystallization to occur at the temperature    used. Preferred crystallization time's range from about 5 minutes to    about 14 days. Thereafter, the crystals are separated from the    liquid and recovered.

Non-limiting examples of various combinations of W, X, Y, and Zcontemplated for the non-layered inorganic porous crystalline phasematerial are disclosed in Table 1.

TABLE 1 Non-Layered Inorganic Porous Crystalline Phase MaterialComponents Component W Component X Component Y Component Z — Al Si — —Al — P — — Si P Co Al — P Co Al Si P — — Si —

The compositions may also include the combinations of W comprising Mg oran element selected from the divalent first row transition metalsincluding Mn, Co and Fe; X comprising B, Ga or Fe; and Y comprising Ge.

The preferred organic directing agent for use in synthesizing thenon-layered inorganic porous crystalline phase material from thereaction mixture is a quaternary ammonium or phosphonium ion of theformula:

wherein Q is nitrogen or phosphorus and wherein at least one of R₁, R₂,R₃, and/or R₄ is aryl or alkyl having from 6 to about 36 carbon atoms,preferably wherein at least one of R₁, R₂, R₃, and/or R₄ comprises—C₆H₁₃, —C₁₀H₂₁, —C₁₆H₃₃, —C₁₈H₃₇, or combinations comprising at leastone of the foregoing. The remainder of R₁, R₂, R₃, and/or R₄ preferablycomprises hydrogen, alkyl of from 1 to 5 carbon atoms, and combinationscomprising at least one of the foregoing. Preferably, the quaternaryammonium or phosphonium ion is derived from the corresponding hydroxide,halide, or silicate.

An additional organic may also be present in the reaction mixture alongwith the above quaternary ammonium or phosphonium. In one embodiment, anadditional organic may be the quaternary ammonium or phosphonium ion ofthe above directing agent formula wherein R₁, R₂, R₃, and R₄ are eachindependently selected from hydrogen and alkyl of 1 to 5 carbon atoms.

Preferred directing agents include cetyltrimethylammonium,cetyltrimethylphosphonium, octadecyltrimethylammonium,octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium,decyltrimethylammonium, dimethyldidodecylammonium, and combinationscomprising at least one of the foregoing.

The support may also be produced using a swelling agent, which mayinclude being pillared to provide materials having a large degree ofporosity. Examples of swelling agents include clays that may be swollenwith water, whereby the layers of the clay are spaced apart by watermolecules. Other materials include those which may be swollen withorganic swelling agents as described in U.S. Pat. No. 5,057,296, and thelike. Organic swelling agents may include amines, quaternary ammoniumcompounds, alkyl and aromatic swelling agents. Preferred swelling agentsinclude alkyl-substituted aromatics such as 1,3,5-trimethylbenzene, andthe like. Examples of non-water swellable layered materials aredescribed in U.S. Pat. No. 4,859,648 and include silicates, magadiite,kenyaite, trititanates and perovskites. Other examples of a non-waterswellable layered materials which can be swollen with organic swellingagents include vacancy-containing titanometallate material, as describedin U.S. Pat. No. 4,831,006.

Once a material is swollen, the material may be pillared by interposinga thermally stable substance, such as silica, between the spaced apartlayers. The aforementioned U.S. Pat. Nos. 4,831,006 and 4,859,648describe methods for pillaring non-water swellable layered materialsdescribed therein, and are incorporated herein by reference fordefinition of pillaring and pillared materials.

Other patents teaching pillaring of materials and the pillared productsinclude U.S. Pat. Nos. 4,216,188; 4,248,739; 4,176,090; and 4,367,163;and European Patent Application 205,711.

The X-ray diffraction patterns of pillared materials can varyconsiderably, depending on the degree that swelling and pillaringdisrupt the otherwise usually well-ordered microstructure. Theregularity of the microstructure in some pillared materials is so badlydisrupted that only one peak in the low angle region on the X-raydiffraction pattern is observed, as a d-spacing corresponding to therepeat distance in the pillared material. Less disrupted materials mayshow several peaks in this region that are generally orders of thisfundamental repeat. X-ray reflections from the crystalline structure ofthe layers are also sometimes observed. The pore size distribution inpillared materials may be narrower than those in amorphous andparacrystalline materials, but may be broader than that in crystallineframework materials.

In producing the support material, the reaction mixture components maybe supplied by more than one source and the reaction mixture may beprepared either batch wise or continuously. Furthermore, the non-layeredinorganic porous crystalline phase material support can be shaped into awide variety of particle sizes and include a powder, a granule, or amolded product, such as an extrudate. In cases where the catalyst ismolded, such as by extrusion, the crystals can be extruded before dryingor partially dried and then extruded.

The particle size of the support is preferably greater than or equal toabout 0.1 micrometers. Within this range, a particle size of less thanor equal to about 100 micrometers can be employed, with less than orequal to about 50 preferred, and less than or equal to about 10 morepreferred. Also preferred within this range is particle size of greaterthan or equal to about 0.5 micrometers, with greater than or equal toabout 0.75 more preferred, and greater than or equal to about 1micrometer especially preferred.

The non-layered inorganic porous crystalline phase material may also becharacterized using techniques that illustrate the microstructure ofthis material, including transmission electron microscopy and electrondiffraction. In determining X-ray diffraction patterns, the X-raydiffraction data is preferably collected using an X-ray diffractionsystem employing theta-theta geometry, Cu K-alpha radiation, and anenergy dispersive X-ray detector such that use of an energy dispersiveX-ray detector eliminates the need for incident or diffracted beammonochromators. Both the incident and diffracted X-ray beams are alsopreferably collimated by double slit incident and diffracted collimationsystems. Preferred slit sizes used, starting from the X-ray tube source,include 0.5, 1.0, 0.3 and 0.2 mm, respectively. However, different slitsystems may produce differing intensities for the peaks in the X-raydiffraction patterns.

Diffraction data may be recorded using step-scanning at 0.04 degrees oftwo-theta, where theta is the Bragg angle, and a counting time of 10seconds for each step is used. The interplanar spacings, d's, may becalculated in Angstrom units (Å), and the relative intensities of thelines, I/I_(o), where I_(o) is one-hundredth of the intensity of thestrongest line, above background, are preferably derived with the use ofa profile fitting routine. Furthermore, the intensities are preferablyuncorrected for Lorentz and polarization effects. It should beunderstood that diffraction data which appears as a single line mayconsist of multiple overlapping lines which under certain conditions,such as very high experimental resolution or crystallographic changes,may appear as resolved or partially resolved lines. Accordingly,crystallographic changes can include minor changes in unit cellparameters and/or a change in crystal symmetry, without a substantialchange in structure. These minor effects, including changes in relativeintensities, can also occur as a result of differences in cationcontent, framework composition, nature and degree of pore filling,thermal and/or hydrothermal history, peak width/shape variations due toparticle size/shape effects, structural disorder, and/or other factorsknown to those skilled in the art of X-ray diffraction.

Properly oriented specimens of the material preferably show a hexagonalarrangement of large channels and the corresponding electron diffractionpattern gives an approximately hexagonal arrangement of diffractionmaxima. As used herein, the d₁₀₀ spacing of the electron diffractionpatterns is the distance between adjacent spots on the hkO projection ofthe hexagonal lattice and is related to the repeat distance a₀ betweenchannels observed in the electron micrographs through the formulad₁₀₀=a₀(3/2)^(1/2). Accordingly, this d₁₀₀ spacing observed in theelectron diffraction patterns corresponds to the d-spacing of a lowangle peak in the X-ray diffraction pattern of the material. Apreparation of the material may include greater than or equal to 20 toabout 40 distinct spots observable in an electron diffraction pattern.These patterns can be indexed with the hexagonal hkO subset of uniquereflections of 100, 110, 200, 210, and the like, and theirsymmetry-related reflections.

The d₁₀₀ may be directly calculated (i.e., determined) from the measuredXRD spectrum, and/or may also be calculated based on one or more peaksin the XRD spectrum. For example, the value of the d₁₀₀ line may becalculated from the d₂₀₀ line based on the formula:d ₁₀₀=2(d ₂₀₀)=2(a ₀(3/2)^(1/2)).

Accordingly, a calculated d₁₀₀ value may be used in the event that thed₁₀₀ value is not directly discernable from the XRD spectrum. As such,the preferred support has a base configuration consistent in manyrespects with the compound referred to as MCM-41, a detailed descriptionof which can be found in U.S. Pat. No. 5,098,684.

The non-layered inorganic porous crystalline phase material support mayalso comprise structural features and attributes of a group ofmesoporous crystalline materials as described in U.S. Pat. Nos.5,198,203 and 5,211,934, to which reference is made for a detaileddescription of these materials, their preparation and properties. Thesematerials may be distinguished by the characteristic X-ray diffractionpattern of the calcined material. Using d₁ to indicate the d-spacings ofthe strongest peak in the X-ray diffraction pattern (relativeintensity=100), the X-ray diffraction pattern of the calcined materialexhibits d₁ at a position greater than about 18 Å d-spacing and at leastone additional weaker peak with d-spacing d₂ such that the ratios ofthese d-spacings relative to d₁ (i.e. d_(n)/d₁) correspond to thefollowing ranges:

d-Spacing d_(n), Å d_(n)/d₁ Relative Intensity d₁ => ~18 1.0 100 d₂ 0.87± 0.06 w − m

More preferably, the X-ray diffraction pattern of the calcined materialincludes at least two additional weaker peaks at d-spacings d₂ and d₃such that the ratios of these d-spacings relative to the strongest peakd₁ at a position greater than about 18 Å d-spacing) correspond to thefollowing ranges:

d-Spacing d_(n), Å d_(n)/d₁ Relative Intensity d₁ => ~18 1.0 100 d₂ 0.87± 0.06 w − m d₃ 0.52 ± 0.04 w

Still more preferably, the X-ray diffraction pattern of the calcinedmaterials includes at least four additional weaker peaks at d-spacingsd₂, d₃, d₄ and d₅ such that the ratios of these d-spacings relative tothe strongest peak d₁ (at a position greater than about 18 Å d-spacing)correspond to the following ranges:

d-Spacing d_(n), Å d_(n)/d₁ Relative Intensity d₁ => ~18 1.0 100 d₂ 0.87± 0.06 w − m d₃ 0.55 ± 0.02 w d₄ 0.52 ± 0.01 w d₅ 0.50 ± 0.01 w

Calcined materials of this group preferably exhibit an X-ray diffractionpattern including at least two peaks at positions corresponding to thefollowing ranges:

d-Spacing d_(n), Å Relative Intensity 33.0 ± 2.0 100 28.7 ± 1.5 w

More preferably, the X-ray diffraction patterns of the calcined examplespresented herein can be characterized as including at least three peaksat positions corresponding to the following ranges:

d-Spacing d_(n), Å Relative Intensity 33.0 ± 2.0 100 28.7 ± 1.5 w 17.2 ±1.2 w

Still more preferably, the X-ray diffraction patterns can becharacterized as including at least five peaks at positionscorresponding to the following ranges

d-Spacing d_(n), Å Relative Intensity 33.0 ± 2.0 100 28.7 ± 1.5 w 18.2 ±0.5 w 17.2 ± 0.4 w 16.5 ± 0.3 w

The honeycomb microstructure of the non-layered inorganic porouscrystalline phase material may also include several moietiesinterconnected in a three dimensional matrix or lattice having largehexagonal channels forming the ultra large pores of the catalyst. Therepeating units forming the large ring structure of the lattice varywith pore size. In addition, a support may comprise 5 to 95 wt. %silica, clay and/or an alumina binder.

The term “hexagonal” is intended to encompass not only materials thatexhibit mathematically perfect hexagonal symmetry within the limits ofexperimental measurement, but also those with significant observabledeviations from that ideal state. A working definition as applied to themicrostructure of the present invention would be that six nearestneighbor channels at roughly the same distance would surround mostchannels in the material. However, defects and imperfections may causesignificant numbers of channels to violate this criterion to varyingdegrees, depending on the quality of the material's preparation. Sampleswhich exhibit as much as +/−25% random deviation from the average repeatdistance between adjacent channels still clearly give recognizableimages of the present ultra-large pore materials. Comparable variationsare also observed in the d₁₀₀ values from the electron diffractionpatterns.

Preferably, the average pore diameter of the non-layered inorganicporous crystalline phase material support may vary from about 20 Å toabout 500 Å. Within this range, a pore diameter of less than or equal toabout 400 Å can be employed, with less than or equal to about 300 Å morepreferred. Also preferred within this range is a pore diameter ofgreater than or equal to about 70 Å, with greater than or equal to about150 Å more preferred. In another embodiment the average pore diameter ofthe support is about 70 Å to about 90 Å.

In a preferred embodiment, the calcined inorganic, non-layeredcrystalline support material of the present invention may also becharacterized as having a more narrowed pore diameter (relative to otherforms of the support) of about 70 Å to about 90 Å. Within this range, apore diameter of less than or equal to about 85 Å can be employed, withless than or equal to about 82 Å more preferred. Also preferred withinthis range is a pore diameter of greater than or equal to about 75 Å,with greater than or equal to about 80 Å more preferred.

Furthermore, the support material, preferably calcined, of the presentinvention preferably has a pore wall thickness of less than or equal toabout 25 Å. Within this range, a pore wall thickness of less than orequal to about 20 Å can be employed, with less than or equal to about 15Å more preferred. Also preferred within this range is a pore wallthickness of greater than or equal to about 1 Å, with greater than orequal to about 4 Å more preferred and greater than or equal to about 6 Åespecially preferred. In a preferred embodiment the pore wall thicknessis from about 1 to 25 Å, preferably, 2 to 25 Å, more preferably 3 to 25Å, more preferably 4 to 23 Å, more preferably 5 to 20 Å, more preferably5 to 18 Å, more preferably 6 to 15 Å.

The calcined support material of the non-layered inorganic porouscrystalline phase material preferably has a uniformity of pore size,wherein greater than or equal to about 80% of the pores have a porediameter plus or minus about 20% the average pore diameter of thesupport; more preferably, greater than or equal to about 90% of thepores present have a pore diameter plus or minus about 5% the averagepore diameter of the support.

In a preferred embodiment, at least about 80% of the pores, based on thetotal number of pores present, have an average pore size greater than orequal to about 70 Å, and less than or equal to about 90 Å. Furthermore,greater than or equal to about 90% of the pores having an average poresize greater than or equal to about 70 Å, and less than or equal toabout 90 Å is more preferred, with greater than or equal to about 95% ofthe pores having an average pore size greater than or equal to about 70Å, and less than or equal to about 90 Å being especially preferred.

Preferred catalyst systems described herein typically have a surfacearea greater than or equal to about 300 m²/g support. Preferred calcinedinorganic, non-layered crystalline support materials of the presentinvention are also characterized as having a total surface area greaterthan or equal to about 300 square meters per gram of support (m²/gsupport).

Accordingly, the support may be characterized as comprising, aftercalcination, a substantially hexagonal arrangement of essentiallyuniform-sized pores. This material exhibits a hexagonal electrondiffraction pattern that can be indexed with a d₁₀₀ value greater thanabout 18 Å.

The support material, especially in its metal, hydrogen and ammoniumforms can be beneficially converted to other forms by thermal treatment(calcination). This thermal treatment is generally performed by heatingat a temperature of greater than or equal to about 200° C., and lessthan or equal to about 1000° C. Within this range, a temperature of lessthan or equal to about 900° C. can be employed, with less than or equalto about 800° C. preferred, and less than or equal to about 750° C. morepreferred. Also preferred within this range is a temperature of greaterthan or equal to about 300° C., with greater than or equal to about 400°C. more preferred, and greater than or equal to about 500° C. especiallypreferred.

The non-layered inorganic porous crystalline phase material ispreferably calcined for at least 1 minute and generally not longer than20 hours. Within this range, a time of less than or equal to about 15hours can be employed, with less than or equal to about 10 hourspreferred, and less than or equal to about 5 hours more preferred. Alsopreferred within this range is a time of greater than or equal to about30 minutes, with greater than or equal to about 1 hour more preferred,and greater than or equal to about 2 hours especially preferred. Thenon-layered inorganic porous crystalline phase material is preferablycalcined in the presence of an oxidizing gas, with oxygen and air beingmost preferred.

Polymerization Catalyst

The catalyst systems of the present invention comprise a catalyst and asupport comprising a non-layered inorganic porous crystalline phasematerial, preferably calcined at greater than or equal to about 200° C.for greater than or equal to about 1 minute, preferably greater than orequal to 5 minutes, in the presence of an oxidizing gas, wherein thesupport comprises a hexagonal arrangement of uniformly-sized poreshaving an average pore diameter greater than or equal to about 13 Å, anX-ray diffraction pattern having a calculated d₁₀₀ value of greater thanor equal to about 18 Å, an adsorption capacity of greater than or equalto about 15 grams benzene per 100 grams support at 50 torr and at 25°C., and a pore wall thickness of less then or equal to about 25 Å. In apreferred embodiment the catalyst system is calcined at about 500° C. toabout 900° C. for about 0.5 hours (30 minutes) to about 10 hours in thepresence of air.

The catalyst preferably comprises a metal or metal containing compounddisposed on and/or in the support material. The metal compound ispreferably a metal oxide derived from a catalyst precursor comprising aGroup 6 metal, more preferably the catalyst comprises chromium (Cr).

The catalyst system preferably comprises about 0.01 to about 10 weightpercent catalyst, based on the total weight of the catalyst system.Accordingly, the weight percent of the Cr in the catalyst system can beabout 0.01 to about 10 weight percent (wt %), based on the total weightof the catalyst system. Within this range, a Cr wt % of less than orequal to about 5 wt % can be employed, with less than or equal to about2 wt % preferred, and less than or equal to about 1.5 wt % morepreferred. Also preferred within this range is a Cr wt % of greater thanor equal to about 0.05 wt %, with greater than or equal to about 0.1 wt% more preferred, and greater than or equal to about 0.15 wt %especially preferred.

The pores of the support are preferably arranged within the support suchthat a surface of the pores define an inner surface of the supportlocated internal to an outer surface of the support. It is preferredthat the catalyst be uniformly arranged throughout the support. Morepreferably, the concentration of the catalyst disposed or located on theinner surface of the support is greater than a concentration of thecatalyst disposed on the outer surface of the support. In other words,the catalyst is preferably disposed and/or located within the pores ofthe support, as compared to the outer surface of the support particle.

Accordingly, it is preferred that the catalyst be present in the same ora substantially higher concentration “inside” the support than “outside”the support. Inside the support refers to the internal surface area ofthe support granule. Outside the support refers to the external surfaceof the support granule. The total surface area refers to both theinternal and external surface area of the support.

In a preferred catalyst system, substantially all of the catalyst issubstantially evenly dispersed over the total surface area of thesupport, wherein substantially all refers to at least about 75%,preferably greater than 90% of the catalyst present with the support. Inthis context, substantially evenly refers to a situation that in any 25square micron surface or greater of the support, the amount of catalystpresent is within 10% of the amount of catalyst present in any othersurface area of the same size.

The surface of the calcined non-layered inorganic porous crystallinephase material support over which the catalyst is dispersed necessarilyincludes the internal surface of the support, i.e. the open-cellmesopores, as well as the external surface. The external surface ispreferably smaller than the internal surface. The dispersion will bepresent on those surfaces of the catalyst, which are accessible tocatalyst loading and dispersion techniques. The most preferred catalystsystem comprises dispersed catalyst wherein all, or substantially all ofthe catalyst is located inside the mesopores of the support, rather thanon the exterior surface of the support. Accordingly, at least 75%preferably, at least 90%, of the catalyst is present inside themesopores of the support. Further, the catalyst within the mesopores issubstantially evenly dispersed over the total surface area of thesupport. The location of particles can be inferred from X-rayPhotoelectron Spectroscopy (XPS), Low Voltage Scanning ElectronMicroscopy (LVSEM), High Resolution Analytical Electron Microscopy (AEM)measurements, as well as directly measured by Secondary Ion MassSpectroscopy (SIMS), all of which are well known to those skilled in therespective arts.

One way to determine the amount of catalyst disposed on the externalsurface and the internal surface of the support is to measure the ratiosof a component of the catalyst to an element in the support, (hereafter“support element”) such as silica.

For example, the chromium to support element ratio may be determined byX-ray Photoelectron Spectroscopy (XPS) normalizing to hydrogen andmetals. For example, for a support comprising silica, the chromium tosilicon ratio could be measured by XPS for the catalyst system (i.e.,the supported catalyst), and a crushed, pulverized or otherwisemasticated sample of the catalyst system. (The word “crushed” refers toa finely ground solid, such as one that has been ground by mortar andpestal to a fine powder.)

The ratio of the noncrushed (Cr:Si) to crushed (Cr:Si) directlycorrelates to the ratio of catalyst to silicon outside the supportparticles over the catalyst to silicon ratio inside the supportparticles.

By way of example, if the XPS data show the concentration of silicon tobe 16.37% and the concentration of chromium to be 8.04% in a firstsample that is not crushed, the ratio of chromium to silicon in thatsample is 8.04 divided by 16.37 which is 0.491. When the sample iscrushed, if the XPS would show 15.68% silicon and 10.29% chromium, thechromium to silicon ratio in the crushed sample is 10.29 divided by15.68, which is 0.656. In this example, the ratio of chromium outside tochromium inside is then determined by dividing 0.491 by 0.656 to come upwith a final ratio of 0.749. For the purposes of this invention it isassumed that the chromium measured in the crushed samples that is fromthe “external” surface of the support is negligible when included in thetotal chromium present. Similar XPS data can be generated by methodsknown in the art for support materials other than silica and should beanalyzed in the same manner as the silica example above.

Preferably, the ratio of catalyst to support element outside to catalystto support element inside should be about 2.0:1 or less, more preferablyabout 1.5:1 or less, even more preferably about 1.0:1.0, still morepreferred is a ratio of 0.85:1.0 or less. In another embodiment theratio of catalyst to support element outside to catalyst to supportelement inside should be about 1.75:1 or less, more preferably about1.25:1 or less, even more preferably about 0.95:1.0, still morepreferred is a ratio of 0.85:1.0 or less, still more preferred is aratio of 0.75:1.0 or less.

Accordingly, in a preferred catalyst system, the pores of the supportare arranged within the support such that a surface of the pores definean inner surface of the support located internal to an outer surface ofthe support, and an amount of the catalyst on the inner surface of thesupport is greater than an amount of the catalyst on the outer surfaceof the support, as determined by comparing the catalyst concentration onessentially the surface of the catalyst system, with the catalystconcentration of an amount of the catalyst system which has beencrushed.

Consistent with the support, the average particle size of the catalystsystem is preferably greater than or equal to about 0.1 micrometers.Within this range, an average particle size of greater than or equal toabout 0.5 micrometers is preferred, with greater than or equal to about1.0 micrometer more preferred.

Preparation of the Catalyst System

The process to prepare the catalyst system of the present inventionpreferably includes preparing a solution or slurry comprising a catalystprecursor, and contacting the catalyst precursor solution with an amountof the support, preferably a non-layered inorganic porous crystallinephase material support. The solvent is then preferably removed from thesupport and the catalyst precursor is then at least partially convertedto the catalyst by calcining the combined precursor and support atgreater than or equal to about 200° C. for greater than or equal toabout 1 minute in the presence of an oxidizing gas to produce thecatalyst system.

The catalytic system is preferably activated by oxidation of thecatalyst precursor by heating (i.e., calcining) at a temperature ofabout 500° C. to about 900° C. in the presence of an oxidizing gas,preferably air. The catalyst may then be treated with a reducing agent(i.e., carbon monoxide), at a temperature and for a period of timesufficient to reduce the metal to a lower valence state, and/or thecatalyst may be reduced through contact with the monomer to bepolymerized during the polymerization process.

The supported metal oxide catalysts are preferably prepared byimpregnating a catalyst precursor onto and into a support using waterand/or an organic solvent. The support material is preferably at leastpartially dehydrated and/or calcined prior to deposition of thecatalytic precursor. This can be done by heating to a temperature in therange of 200° C. to 900° C. in an atmosphere such as air, nitrogen, orboth, at atmospheric, subatmospheric or superatmospheric pressures for aperiod of time between about 30 minutes and about 48 hours. Dehydrationcan also be performed at room temperature merely by placing thecomposition in a vacuum, but a longer time is required to obtain asufficient amount of dehydration.

Preferably the catalyst precursor comprises chromium. Examples ofpreferred catalyst precursors for a catalyst comprising chromium includechromic acetate, chromic bromide, chromic carbonate, chromic chloride,chromic fluoride, chromic formate, chromic hydroxide, chromic nitrate,chromic oxide, chromic phosphate, chromic potassium sulfate, chromicsulfate, chromium metal, chromium carbonyl, chromium dioxide, chromiumpicolinate, chromium tetrafluoride, chromium trioxide, chromiumacetylacetonate, chromous acetate, chromous bromide, chromous chloride,chromous fluoride, chromous formate, chromous oxalate, chromous sulfate,chromyl chloride, chromyl fluoride, or a combination comprising at leastone of the foregoing. Suitable organic solvents depend on the catalystprecursor used, and may include ethanol, methanol, and/or acetic acid.

In a preferred embodiment, the catalyst is contacted with the supportusing an incipient wetness technique, wherein the solution or slurrycomprises a catalyst precursor, preferably comprising chromium, whichcomprises an amount of solvent less than or equal to about twice thetotal pore volume of the amount of the support. Preferably the amount ofsolvent is less than or equal to the total pore volume of support, withan amount of solvent less than the total pore volume of the supportbeing more preferred. The precursor solution is then contacted with anamount of the support, preferably a non-layered inorganic porouscrystalline phase material support. The solvent is then preferablyremoved from the support and the catalyst precursor is then at leastpartially converted to the catalyst by calcining the combined precursorand support at greater than or equal to about 200° C. for greater thanor equal to about 1 minute in the presence of an oxidizing gas toproduce the catalyst system.

Monomers

The catalyst systems of this invention may be used to polymerize and/oroligomerize any unsaturated monomer or monomers. Preferred monomersinclude C₂ to C₁₀₀ olefins, more preferably C₂ to C₆₀ olefins, stillmore preferably C₂ to C₄₀ olefins, with preferably C₂ to C₂₀ olefinsstill more preferred, and C₂ to C₁₂ olefins being most preferred. Insome embodiments monomers include linear, branched or cyclicalpha-olefins, preferably C₂ to C₁₀₀ alpha-olefins, more preferably C₂to C₆₀ alpha-olefins, still more preferably C₂ to C₄₀ alpha-olefins,with C₂ to C₂₀ alpha-olefins being more preferred, and C₂ to C₁₂alpha-olefins most preferred. Examples of preferred olefin monomersinclude one or more of ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl hexene-1, and 5-ethyl-1-nonene.

The polymer produced herein may be a copolymer of one or more linear orbranched C₃ to C₃₀ prochiral alpha-olefins, or C₅ to C₃₀ ring containingolefins or combinations thereof capable of being polymerized by eitherstereospecific and non-stereospecific catalysts. Prochiral, as usedherein, refers to monomers that favor the formation of isotactic orsyndiotactic polymer when polymerized using stereospecific catalyst(s).

Preferred monomers may also include aromatic-group-containing monomerscontaining up to about 30 carbon atoms. Suitablearomatic-group-containing monomers comprise at least one aromaticstructure, preferably from one to three, more preferably a phenyl,indenyl, fluorenyl, or naphthyl moiety. The aromatic-group-containingmonomer may further comprise at least one polymerizable double bond suchthat after polymerization, the aromatic structure will be pendant fromthe polymer backbone. The aromatic-group containing monomer may furtherbe substituted with one or more hydrocarbyl groups including, but notlimited to, C₁ to C₁₀ alkyl groups. Additionally, two adjacentsubstitutions may be joined to form a ring structure. Preferredaromatic-group-containing monomers contain at least one aromaticstructure appended to a polymerizable olefinic moiety. Particularlypreferred aromatic monomers include styrene, alpha-methylstyrene,para-alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl benzene, andindene, especially styrene, paramethyl styrene, 4-phenyl-1-butene, andallyl benzene.

Non-aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to about 30 carbon atoms. Suitable non-aromaticcyclic group containing monomers preferably have at least onepolymerizable olefinic group that is either pendant on the cyclicstructure or is part of the cyclic structure. The cyclic structure mayalso be further substituted by one or more hydrocarbyl groups such as,but not limited to, C₁ to C₁₀ alkyl groups. Preferred non-aromaticcyclic group containing monomers include vinylcyclohexane,vinylcyclohexene, vinylnorbornene, ethylidene norbornene,cyclopentadiene, cyclopentene, cyclohexene, cyclobutene,vinyladamantane, and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, and triacontadiene. Particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins, with or withoutsubstituents at various ring positions.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the olefin(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

The process described herein may be used to produce an oligomer of anyof the monomers listed above. Preferred oligomers include oligomers ofany C₂ to C₂₀ olefins, preferably C₂ to C₁₂ alpha-olefins, mostpreferably oligomers comprising ethylene, propylene and or butene areprepared. A preferred feedstock for the oligomerization process is thealpha-olefin, ethylene. Other alpha-olefins, including but not limitedto propylene and 1-butene, may also be used alone or combined withethylene. Preferred alpha-olefins include any C₂ to C₄₀ alpha-olefin,preferably and C₂ to C₂₀ alpha-olefin, preferably any C₂ to C₁₂alpha-olefin, preferably ethylene, propylene, and butene, mostpreferably ethylene. Dienes may be used in the processes describedherein, preferably alpha, omega-dienes are used alone or in combinationwith mono-alpha olefins.

The process described herein may be used to produce homopolymers orcopolymers. As used herein, a copolymer may comprise two, three, four ormore different monomer units. Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.The polymer may be a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In stillanother embodiment, the polymer is a copolymer comprising propylene andone or more of any of the monomers listed above.

The polymer produced herein may be a copolymer of ethylene and one ormore C₃ to C₂₀ linear, branched or cyclic monomers, preferably one ormore C₃ to C₁₂ linear, branched or cyclic alpha-olefins. Preferably, thepolymer produced herein is a copolymer of ethylene and one or more ofpropylene, butene, pentene, hexene, heptene, octene, nonene, decene,dodecene, 4-methyl-pentene-1,3-methyl pentene-1, and 3,5,5-trimethylhexene-1.

The polymer produced herein may be a copolymer of propylene and one ormore C₂ or C₄ to C₂₀ linear, branched or cyclic monomers, preferably oneor more C₂ or C₄ to C₁₂ linear, branched or cyclic alpha-olefins. Thepolymer produced herein may also be a copolymer of propylene and one ormore of ethylene, butene, pentene, hexene, heptene, octene, nonene,decene, dodecene, 4-methyl-pentene-1,3-methyl pentene-1, and3,5,5-trimethyl hexene-1.

The copolymers described herein may comprise at least 50 mole % of afirst monomer and up to 50 mole % of other monomers. In anotherembodiment, the polymer comprises: a first monomer present at from 40 to95 mole %, preferably 50 to 90 mole %, preferably 60 to 80 mole %; acomonomer present at from 5 to 40 mole %, preferably 10 to 60 mole %,more preferably 20 to 40 mole %; and a termonomer present at from 0 to10 mole %, more preferably from 0.5 to 5 mole %, more preferably 1 to 3mole %.

In a preferred embodiment, the first monomer comprises one or more ofany C₂ to C₈ linear branched or cyclic alpha -olefins, includingethylene, propylene, butene, (and all isomers thereof), pentene (and allisomers thereof), hexene (and all isomers thereof), heptene (and allisomers thereof), and octene (and all isomers thereof). Preferredmonomers include ethylene, propylene, 1-butene, 1-hexene, 1-octene,cyclohexene, cyclooctene, hexadiene, cyclohexadiene and the like. Thecomonomer comprises one or more of any C₂ to C₄₀ linear, branched orcyclic alpha-olefins (provided ethylene, if present, is present at 5mole % or less), including ethylene, propylene, butene, pentene, hexene,heptene, and octene, nonene, decene, un-decene, do-decene, hexadecene,butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene,decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene. The termonomer comprises one or moreof any C₂ to C₄₀ linear, branched or cyclic alpha-olefins, (providedethylene, if present, is present at 5 mole % or less), includingethylene, propylene, butene, pentene, hexene, heptene, and octene,nonene, decene, un-decene, do-decene, hexadecene, butadiene, hexadiene,heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene,styrene, 3,5,5-trimethyl hexene-1,3-methylpentene-1,4-methylpentene-1,cyclopentadiene, and cyclohexene.

The polymers described above may further comprise one or more dienes atup to about 10 weight %, preferably at 0.00001 to 1.0 weight %,preferably 0.002 to 0.5 weight %, even more preferably 0.003 to 0.2weight %, based upon the total weight of the composition. In someembodiments, 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Polymerization Processes

The catalyst compositions described above may be used to oligomerize orpolymerize any unsaturated monomer, typically alpha-olefins. One or morecatalyst systems as described herein, and one or more monomers arecontacted to produce a polymer. Accordingly, a preferred process topolymerize an unsaturated monomer, comprises contacting the monomer witha catalyst system and optionally a scavenger, wherein the catalystsystem comprises a catalyst and a support comprising a non-layeredinorganic porous crystalline phase material calcined at greater than orequal to about 200° C. for greater than or equal to about 1 minute inthe presence of an oxidizing gas, wherein the support comprises ahexagonal arrangement of uniformly-sized pores having an average porediameter greater than or equal to about 13 Å, an X-ray diffractionpattern having a calculated d₁₀₀ value of greater than or equal to about18 Å, an adsorption capacity of greater than or equal to about 15 gramsbenzene per 100 grams support at 50 torr and at 25° C., and a pore wallthickness of less then or equal to about 25 Å.

Preferred scavengers for use herein include triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like.

The components may be contacted in a solution, bulk, gas or slurrypolymerization process or a combination thereof, preferably gas phase orslurry polymerization process. Thus the present invention furtherrelates to a process to produce polymers from the monomers hereindescribed. The combined catalyst system and monomer are preferablycombined in ratios of about 1:1,000,000 to about 10:1.

One or more reactors in series or in parallel may be used in the presentinvention. The catalyst system is preferably delivered as a slurry or asa powder to the reactor. Polymerizations are carried out in eithersingle reactor operation, in which monomer, comonomers, catalyst,scavenger, and optional modifiers are added continuously to a singlereactor or in series reactor operation, in which the above componentsare added to each of two or more reactors connected in series. Thecatalyst components can be added to the first reactor in the series. Thecatalyst component may also be added to both reactors, with onecomponent being added to first reaction and another component to otherreactors.

The catalytic activity of the catalyst system towards polymerization ofethylene may be determined under polymerization conditions of about 1liter of isobutane, about 0.25 mmol of dibutylmagnesium, and about 100mg of catalyst at a total pressure of about 450 psig (3103 KPa) to about500 psig (3447 KPa), and at a temperature of about 100° C. to about 110°C. Under these conditions, the activity of the catalyst system in g/g/hris preferably greater than or equal to about 800 g/g/hr for ethylene.

The resultant catalyst system demonstrates improved activity (relativeto known catalyst systems) for polymerizing olefins at a temperaturerange from below room temperature, up to and including about 250° C.Within this range, a temperature of less than or equal to about 200° C.can be employed, with less than or equal to about 150° C. preferred, andless than or equal to about 115° C. more preferred. Also preferredwithin this range is a temperature of greater than or equal to about 50°C., with greater than or equal to about 70° C. more preferred, andgreater than or equal to about 90° C. especially preferred.

The polymerization pressure can be sub atmospheric (i.e., less than 1atmosphere) to about 5,000 psig (34,474 KPa). Within this range, apressure of less than or equal to about 1,000 psig (6,895 KPa) can beemployed, with less than or equal to about 800 psig (5,516 KPa)preferred, and less than or equal to about 700 psig (4,826 KPa) morepreferred. Also preferred within this range is a pressure of greaterthan or equal to about 100 psig (689 KPa), with greater than or equal toabout 200 psig (1,379 KPa) more preferred, and greater than or equal toabout 250 psig (1,724 KPa) especially preferred.

The induction time, as used herein, is defined as the period of timebetween contacting the olefin, the catalyst, and optionally a scavengerunder polymerization conditions, and when an appreciable amount ofpolymer begins to be produced (e.g., a detectable consumption of monomerin the polymerization process also referred to as olefin uptake).Induction time is preferably less than 5 minutes. Preferably, aninduction time of less than or equal to about 3 minutes can be employed,with less than or equal to about 2 minutes preferred, and less than orequal to about 1 minute more preferred. Further, the catalyst systemused herein may be employed in a batch type reactor, a fixed bedreactor, a slurry reactor, gas phase reactor, and/or in acontinuous-flow reactor.

Preferably the induction time between contacting of the monomer with thecatalyst system, and the onset of polymerization, is less than or equalto about 2 minutes for ethylene polymerization at about 100° C. to about110° C., and about 450 psig to about 500 psig.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661 and 5,668,228 all of which are fullyincorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment when high-density polyethylene is desired then the reactortemperature is typically between 70 and 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 to 90 mole percent and thecomonomer partial pressure is in the range of from about 138 kPa toabout 517 kPa, preferably about 517 kPa to about 2069 kPa, which aretypical conditions in a gas phase polymerization process. Also in somesystems the presence of comonomer can increase productivity.

In a preferred embodiment, the reactor utilized in the present inventionis capable of producing more than 500 lbs of polymer per hour (227Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 andEP-B-634 421, all of which are herein fully incorporated by reference.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psi to 735 psi, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andoptionally comonomers along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process shouldbe operated above the reaction diluent critical temperature andpressure. Preferably, a hexane or an isobutane medium is employed.

Useful polymerization techniques include those referred to as particleform polymerization, or slurry process. Such technique are known, anddescribed in for instance, in U.S. Pat. No. 3,248,179, which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

The slurry process may be carried out continuously in a loop reactor.The catalyst, as a slurry in isobutane or as a dry free flowing powder,is injected regularly to the reactor loop, which is itself filled withcirculating slurry of growing polymer particles in a diluent ofisobutane containing monomer and comonomer.

Hydrogen, optionally, may be added as a molecular weight control. Thereactor is maintained at a pressure of 3620 kPa to 4309 kPa and at atemperature in the range of about 60° C. to about 104° C. depending onthe desired polymer melting characteristics. Reaction heat is removedthrough the loop wall since much of the reactor is in the form of adouble-jacketed pipe. The slurry is allowed to exit the reactor atregular intervals or continuously to a heated low-pressure flash vessel,rotary dryer and a nitrogen purge column in sequence for removal of theisobutane diluent and all unreacted monomer and comonomers. Theresulting hydrocarbon free powder is then compounded for use in variousapplications.

The reactor used in the slurry process of the invention may be capableof producing greater than 2000 lbs of polymer per hour (907 Kg/hr), morepreferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferablygreater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment theslurry reactor used in the process of the invention is producing greaterthan 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greaterthan 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500Kg/hr).

Using the slurry process of the invention, the total reactor pressuremay be in the range of from 400 psig (2758 kPa) to 800 psig (5516 kPa),preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa), morepreferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In the slurry process of the invention, the concentration of predominantmonomer in the reactor liquid medium may be in the range of from about 1to 10 weight percent, preferably from about 2 to about 7 weight percent,more preferably from about 2.5 to about 6 weight percent, mostpreferably from about 3 to about 6 weight percent.

The process, preferably a slurry or gas phase process may be operated inthe absence of or essentially free of any scavengers, such astriethylaluminum, trimethylaluminum, tri-isobutylaluminum andtri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and thelike. This process is described in PCT publication WO 96/08520 and U.S.Pat. No. 5,712,352, which are herein fully incorporated by reference.The process described herein may also be run with scavengers.

Bulk or Solution Phase Polymerization

The catalysts described herein can be used advantageously in solutionprocesses ( i.e. one where the polymer is soluble in the reactionmedium. Generally this involves polymerization in a continuous reactorin which the polymer formed and the starting monomer and catalystmaterials supplied, are agitated to reduce or avoid concentrationgradients. Suitable processes operate above the melting point of thepolymers at high pressures (i.e., from about 1 to about 3000 bar(10-30,000 MPa)), in which the monomer acts as diluent or in solutionpolymerization using a solvent.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 0° C. and about 160° C., more preferably from about10° C. to about 140° C., and most preferably from about 40° C. to about120° C. In series operation, the second reactor temperature ispreferably higher than the first reactor temperature. In parallelreactor operation, the temperatures of the two reactors are independent.The pressure can vary from about 1 mm Hg to 2500 bar (25,000 MPa),preferably from 0.1 bar to 1600 bar (1-16,000 MPa), most preferably from1.0 to 500 bar (10-5000 MPa).

Each of these processes may also be employed in a single reactor, or ina parallel or series reactor configuration. The liquid processescomprise contacting olefin monomers with the above described catalystsystem in a suitable diluent or solvent and allowing said monomers toreact for a sufficient time to produce the desired polymers. Hydrocarbonsolvents are suitable, both aliphatic and aromatic. Alkanes, such ashexane, pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor or plug flow reactor, or more than one reactor operated inseries or parallel. These reactors may have or may not have internalcooling and the monomer feed my or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, international application WO 96/33227 and WO97/22639.

Polymers Produced

The polymers produced herein, particularly the ethylene homopolymers andcopolymers, may have a weight average molecular weight (Mw) of 25,000 to500,000. The polymers produced herein, particularly the ethylenehomopolymers and copolymers, may also have a molecular weightdistribution (Mw/Mn) of up to 35, more preferably of up to 30 morepreferably from 2 to 30, more preferably from 2 to 25.

The polymers produced by this invention are preferably high densitypolyethylene, defined as polyethylene having a density greater than orequal to about 0.9 grams per cubic centimeter of polymer. Polymerizationof ethylene to produce polyethylene having a density of greater than orequal to about 0.94 is preferred, with production of polyethylene havinga density greater than or equal to about 0.95 being especiallypreferred.

Polymers or oligomers produced by this invention may be functionalized.Preferred functional groups include maleic acid and maleic anhydride. Byfunctionalized is meant that the polymer has been contacted with anunsaturated acid or anhydride. Preferred unsaturated acids or anhydridesinclude any unsaturated organic compound containing at least one doublebond and at least one carbonyl group. Representative acids includecarboxylic acids, anhydrides, esters and their salts, both metallic andnon-metallic. More preferably, the organic compound contains anethylenic unsaturation conjugated with a carbonyl group (—C═O). Examplesinclude maleic, fumaric, acrylic, methacrylic, itaconic, crotonic,alpha.methyl crotonic, and cinnamic acids as well as their anhydrides,esters and salt derivatives. Maleic anhydride is particularly preferred.The unsaturated acid or anhydride is preferably present at about 0.1weight % to about 10 weight %, preferably at about 0.5 weight % to about7 weight %, even more preferably at about 1 to about 4 weight %, basedupon the weight of the hydrocarbon resin and the unsaturated acid oranhydride.

EXAMPLES Example 1

Preparation of 89 Å Support

The synthesis method of this material may be similar to that describedby Beck, et. al., JACS, 114(27) (1992), 10832 and in U.S. Pat. No.5,057,296, Example 41. In particular, a cetyltrimethylammonium hydroxide(CTMAOH) solution is prepared by contactingN,N,N-trimethyl-1-hexadecanaminium chloride solution with ahydroxide-for-halide exchange resin. An amount of sodium aluminate(NaAlO₂) was added to the mixture, which is then stirred until theNaAlO₂ is completely dissolved. To this solution is addedtetramethylammonium (TMA) silicate solution, silica, water, and1,3,5-trimethylbenzene. The resulting mixture is then stirred at roomtemperature for several minutes to produce a gel. The gel is then loadedinto a stirred autoclave and heated at about 105° C. for about 3 days.The resulting product is filtered and washed several times with warm(60-70° C.) distilled water and with acetone. The support is thencalcined to about 538° C. in a N₂/air mixture and then held in air forabout 10 hours.

The XRD pattern of the resulting material prepared as described aboveindicated a d-spacing of the d₁₀₀ peak at about 82 Å. Based on thehexagonal indexing of this material, this corresponds to a repeatdistance between pores of about 95 Å (d₁₀₀×2/√{square root over (3)}).The average pore size, taken from the BJH adsorption plot, was about 89Å. The difference between these two numbers represents a wall thicknessof about 6 Å.

Preparation of Catalyst System Using 89 Å Support

0.116 g of (CH₃CO₂)₇Cr₃(OH)₂ were dissolved in 4.5 mL of H₂O. Thesolution was added dropwise to 3.00 g of the above 89 Å support. Themixture was well blended and then dried in a vacuum oven at about 70° C.for about 20 hrs. The resulting catalyst precursor was activated in dryair at about 870° C. to afford the polymerization catalyst.

Comparative Example 1

Preparation of 95 Å Support

30 grams of DI H₂O, 120 grams of 2M HCl, 4.0 grams of triblock copolymerPluronic P123 (EO₂₀PO₇₀EO₂₀), and 3.0 grams of 1,3,5 trimethylbenzenewere combined with mixing. To this mixture 8.5 grams oftetraethylorthosilicate was added and the combined mixture was heated to35° C. for 20 hours with stirring. The temperature was raised to 100° C.and the stirring was stopped. After 24 hours at 100° C., the mixture wascooled and the sample was filtered and washed with DI H₂O. A portion ofthe material was calcined to 500° C. in air for 3 hours and theresultant calcined material was analyzed. The calcined sample had a poresize of about 95 Å (BJH adsorption plot), surface area of 793 m²/g, anda pore volume of 1.33 g/cc.

The XRD pattern indicated a d-spacing of the d₁₀₀ peak at about 55 Å,representing a repeat distance between pores of about 127 Å (2d₂₀₀×2/{square root over (3)}) based on the hexagonal indexing of thismaterial. The average pore size taken from the BJH adsorption plot wasabout 95 Å. The difference between these two values represents a porewall thickness of about 32 Å.

Preparation of Catalyst System Using 95 Å Support

This catalyst was prepared in a manner similar to that in Example 1except the above described 95 Å support was used.

Comparative Example 2

Preparation of 62 Å Support

30 grams of DI H₂O, 120 grams of 2M HCl, and 4.0 grams of triblockcopolymer Pluronic P123 (EO₂₀PO₇₀EO₂₀) was combined with mixing. To thismixture 8.5 grams of tetraethylorthosilicate was added and the combinedmixture was heated to 35° C. for 20 hours with stirring. The temperaturewas raised to 100° C. and the stirring was stopped. After 24 hours at100° C., the mixture was cooled and the sample was filtered and washedwith DI H₂O. A portion of the material was calcined to 500° C. in airfor 3 hours and the resultant calcined material was analyzed. Thecalcined sample had a pore size of about 62 Å (BJH adsorption plot),surface area of 820 m²/g, and a pore volume of 0.93 g/cc.

The XRD pattern indicated a d-spacing of the d₁₀₀ peak at about 46 Å,corresponding to a repeat distance between pores of about 106 Å(2×d₂₀₀×2/{square root over (3)}), based on the hexagonal indexing ofthis material. The average pore size taken from the BJH adsorption plotwas about 62 Å. The difference between these two values represents apore wall thickness of about 44 Å.

Preparation of Catalyst System Using 62 Å Support

This catalyst was prepared in a manner similar to that in Example 1except 3.0 mL of H₂O were used to produce the solution and the abovedescribed 62 Å support was used.

Comparative Example 3

Preparation of Catalyst system using 969 MPI

969 MPI is a silica supported chromium catalyst available from W.R.Grace & Co. This catalyst was activated in dry air at 870° C. to affordthe polymerization catalyst.

Ethylene Polymerization

Ethylene polymerization was carried out in a 2 L Zipperclave reactor(Autoclave Engineering). First, the reactor was purged under a nitrogenflow for 2 hrs at 120-140° C. Hexane and/or 1-hexene solutions ofdibutylmagnesium (DBM), and hydrogen as required were added to 850 mL ofisobutane and charged to the reactor. The reactor was then heated to105-110° C. and pressurized with ethylene to a total pressure of 470psig (3,241 kPa). 100 mg of catalyst was then charged to the reactor viaslurry addition of the remaining 150 mL of isobutane. Duringpolymerization, the reactor temperature was controlled via thermocouplesin the reactor and the external jacket. Ethylene was fed on demand tomaintain the desired total pressure. The polymerization was terminatedafter 45 min by removing heat, and venting the volatiles.

Test Methods

I₂ (g/10 minute) was determined according to ASTM D1238-95, Condition E(2.16 kg, 190° C.).

I₂₁ (g/10 minute) was determined according to ASTM D1238-95, Condition F(2.16 kg, 190° C.).

Density (g/cm³) was determined according to ASTM D1505-98.

Induction time (minutes) was determined using a stopwatch to measuringthe time elapsed between catalyst charged to the reactor, and adetectable onset of ethylene uptake, which was less than or equal toabout 0.1 standard liter/minute ethylene flow using a mass flow meterwith this particular set-up. Pore size was determined using the BJHadsorption model, see for example Barrett, E. P., Joyner, L. G. andHalenda, P. P., 1951 “The Determination of Pore Volume and AreaDistributions in Porous Substances; I. Computations from NitrogenIsotherms”; J. Amer. Chem. Soc. 73, 373-380.

The examples for ethylene polymerization and copolymerization using theabove examples and comparative examples are presented in Table 2,Supported Cr Catalyst For Ethylene Polymerization.

TABLE 2 Supported Cr Catalyst for Ethylene Polymerization Support Al₂O₃1-Hexene Hydrogen Reactor T Ind. Time Activity I₂ I₂₁ Density Run IDPore size Wt % mL mmol ° C. Min g/g/hr g/10 min g/10 min g/cm³ Ex. 1 89Å 4.5 0.00 0 105 0 1820 0.00 0.77 0.9519 Ex. 1 89 Å 4.5 0.75 0 105 11497 0.01 2.38 0.9504 Ex. 1 89 Å 4.5 0.00 60 105 1 832 0.01 5.16 0.9557Ex. 1 89 Å 4.5 0.75 60 105 1 1037 0.00 2.76 0.9526 Ex. 1 89 Å 4.5 0.00 0107 2 1701 0.00 1.89 0.9506 Ex. 1 89 Å 4.5 0.75 0 107 1 1487 0.02 4.280.9469 C-Ex. 1 95 Å 0 0.00 0 105 16 268 0.00 0.29 C-Ex. 1 95 Å 0 0.75 0105 15 303 C-Ex. 1 95 Å 0 0.00 0 107 10 492 C-Ex. 1 95 Å 0 0.75 0 107 17350 0.00 0.21 C-Ex. 2 62 Å 0.00 0 105 10 83 C-Ex. 2 62 Å 0 0.75 0 105 1442 0.00 0.38 C-Ex. 2 62 Å 0 0.00 0 107 — 104 C-Ex. 2 62 Å 0 0.75 0 107 6103 C-Ex. 3 969 MPI 0 0.00 0 105 8 1188 0.05 11.98 0.9525 C-Ex. 3 969MPI 0 0.75 0 105 7 1288 0.16 19.56 0.9490 C-Ex. 3 969 MPI 0 0.00 60 1055 1235 0.80 55.08 0.9492 C-Ex. 3 969 MPI 0 0.75 60 105 5 730 0.73 64.620.9497 C-Ex. 3 969 MPI 0 0.00 0 107 15 949 0.19 16.13 0.9505 C-Ex. 3 969MPI 0 0.75 0 107 10 1087 0.22 20.64 0.9470

All catalysts were activated at 870° C. Polymerization conditions were:0.25 mmol DBM in 1 liter isobutane, 470 psig (3,241 kPa) total pressure,45 min. run time.

In comparison with commercially available 969 MPI (Comparative Example3) under a variety of conditions, Example 1 using 89 Å supportdemonstrated lower induction time and higher catalyst activity relativeto the Comparative Examples 1, 2, and 3 evaluated.

Accordingly, disclosed herein is:

-   -   1A. A catalyst system comprising a catalyst and non-layered        inorganic porous crystalline phase material, wherein the support        comprises a hexagonal arrangement of uniformly-sized pores        having an average pore diameter greater than or equal to about        13 Å, an X-ray diffraction pattern having a calculated d₁₀₀        value of greater than or equal to about 18 Å, an adsorption        capacity of greater than or equal to about 15 grams benzene per        100 grams support at 50 torr and at 25° C., and a pore wall        thickness of less then or equal to about 25 Å.    -   2A. The catalyst system of 1A above, wherein the support is        calcined at greater than or equal to about 200° C. for greater        than or equal to about 1 minute in the presence of an oxidizing        gas.    -   3A. The catalyst system of 1A or 2A above, wherein the support        is calcined at about 500° C. to about 750° C. for about 0.5 to        about 10 hours in air.    -   4A. The catalyst system of 1A-3A above, wherein greater than or        equal to about 80% of the pores have a pore diameter plus or        minus about 20% the average pore diameter.    -   5A. The catalyst system of 1A-4A above, wherein greater than or        equal to about 90% of the pores present have a pore diameter        plus or minus about 5% the average pore diameter.    -   6A. The catalyst system of 1A-5A above, wherein the average pore        diameter is about 20 Å to about 500 Å.    -   7A. The catalyst system of 1A-6A above, wherein the average pore        diameter is about 70 Å to about 90 Å.    -   8A. The catalyst system of 1A-7A above having a surface area        greater than or equal to about 300 m²/g support.    -   9A. The catalyst system of 1A-8A above, wherein the pore wall        thickness is less than or equal to about 20 Å.    -   10A. The catalyst system of 1A-9A above, wherein the pore wall        thickness is greater than or equal to about 4 Å.    -   11A. The catalyst system of 1A-10A above, wherein said        crystalline phase material has a composition expressed as        follows:        M_(n/q)(W_(a)X_(b)Y_(c)Z_(d)O_(h))        where M is one or more ions; n is the charge excluding M        expressed as oxides;

-   q is the weighted molar average valence of M;

-   n/q is the number of moles or mole fraction of M;

-   W is one or more divalent elements;

-   X is one or more trivalent elements;

-   Y is one or more tetravalent elements;

-   Z is one or more pentavalent elements;

-   a, b, c, and d are mole fractions of W, X, Y, and Z, respectively;

-   h is a number of from 1 to 2.5; and

-   (a+b+c+d)=1.    -   12A. The catalyst system of 11A, wherein a and d are 0 and h=2.    -   13A. The catalyst system of 12A, wherein X comprises aluminum        and Y comprises silicon.    -   14A. The catalyst system of 13A, comprising about 0.1 to about        20 weight percent alumina, based on the total weight of the        support.    -   15A. The catalyst system of 1A-14A above having an average        particle size greater than or equal to about 1 micrometer.    -   16A. The catalyst system of any of 1A to 15A where the system is        calcined at greater than or equal to about 200° C. for greater        than or equal to about 1 minute in the presence of an oxidizing        gas).    -   17A. The catalyst system of 16A, wherein the catalyst comprises        a Group 6 metal.    -   18A. The catalyst system of 16A-17A above, wherein the catalyst        comprises chromium.    -   19A. The catalyst system of 16A-18A above, wherein the pores of        the support are arranged within the support such that a surface        of the pores define an inner surface of the support located        internal to an outer surface of the support, and wherein an        amount of the catalyst on the inner surface of the support is        greater than an amount of the catalyst on the outer surface of        the support, as determined by comparing the catalyst        concentration on essentially the surface of the catalyst system,        with the catalyst concentration of an amount of the catalyst        system which has been crushed.    -   20A. The catalyst system of 16A-19A above wherein the support is        calcined at about 500° C. to about 750° C. for about 0.5 to        about 10 hours in air.    -   21A. The catalyst system of 16A-20A above, wherein greater than        or equal to about 80% of the pores have a pore diameter plus or        minus about 20% the average pore diameter.    -   22A. The catalyst system of 16A-21A above, wherein greater than        or equal to about 90% of the pores present have a pore diameter        plus or minus about 5% the average pore diameter.    -   23A. The catalyst system of 16A-22A above, wherein the average        pore diameter is about 20 Å to about 500 Å.    -   24A. The catalyst system of 16A-23A above, wherein the average        pore diameter is about 70 Å to about 90 Å.    -   25A. The catalyst system of 16A-24A above having a surface area        greater than or equal to about 300 m²/g support.    -   26A. The catalyst system of 16A-25A above, wherein the pore wall        thickness is less than or equal to about 20 Å.    -   27A. The catalyst system of 26A, wherein the pore wall thickness        is greater than or equal to about 4 Å.    -   28A. The catalyst system of 16A-27A above, wherein said        crystalline phase material has a composition expressed as        follows:        M_(n/q)(W_(a)X_(b)Y_(c)Z_(d)O_(h))        where M is one or more ions; n is the charge excluding M        expressed as oxides;

-   q is the weighted molar average valence of M;

-   n/q is the number of moles or mole fraction of M;

-   W is one or more divalent elements;

-   X is one or more trivalent elements;

-   Y is one or more tetravalent elements;

-   Z is one or more pentavalent elements;

-   a, b, c, and d are mole fractions of W, X, Y, and Z, respectively;

-   h is a number of from 1 to 2.5; and

-   (a+b+c+d)=1.    -   29A. The catalyst system of 28A, wherein a and d are 0 and h=2.    -   30A. The catalyst system of 29A, wherein X comprises aluminum        and Y comprises silicon.    -   31A. The catalyst system of 30A, comprising about 0.1 to about        20 weight percent alumina, based on the total weight of the        support.    -   32A. The catalyst system of 16A-31A above having an average        particle size greater than or equal to about 1 micrometer.    -   33A. The catalyst system of 16A-32A above, comprising about 0.01        to about 10 weight percent catalyst, based on the total weight        of the catalyst system.    -   34A. A process to prepare the catalyst system of 16A-33A above,        comprising    -   contacting a solution comprising a catalyst precursor with an        amount of the support, wherein the solution comprises an amount        of solvent less than or equal to about twice the total pore        volume of the amount of the support;    -   removing the solvent from the support; and    -   preferably, calcining the support at greater than or equal to        about 200° C. for greater than or equal to about 1 minute in the        presence of an oxidizing gas to produce the catalyst system.    -   35A. The process of 34A, wherein the catalyst precursor        comprises chromium.    -   36A. The process of 35A, wherein the catalyst precursor        comprises chromic acetate, chromic bromide, chromic carbonate,        chromic chloride, chromic fluoride, chromic formate, chromic        hydroxide, chromic nitrate, chromic oxide, chromic phosphate,        chromic potassium sulfate, chromic sulfate, chromium metal,        chromium carbonyl, chromium dioxide, chromium picolinate,        chromium tetrafluoride, chromium trioxide, chromium        acetylacetonate, chromous acetate, chromous bromide, chromous        chloride, chromous fluoride, chromous formate, chromous oxalate,        chromous sulfate, chromyl chloride, chromyl fluoride, or a        combination comprising at least one of the foregoing.    -   37A. A process to polymerize an unsaturated monomer, comprising:        contacting the monomer with a catalyst system and optionally a        scavenger, wherein the catalyst system comprises a catalyst and        a support comprising a non-layered inorganic porous crystalline        phase material calcined at greater than or equal to about        200° C. for greater than or equal to about 1 minute in the        presence of an oxidizing gas, wherein the support comprises a        hexagonal arrangement of uniformly-sized pores having an average        pore diameter greater than or equal to about 13 Å, an X-ray        diffraction pattern having a calculated d₁₀₀ value of greater        than or equal to about 18 Å, an adsorption capacity of greater        than or equal to about 15 grams benzene per 100 grams support at        50 torr and at 25° C., and a pore wall thickness of less then or        equal to about 25 Å.    -   38A. The process of 37A, wherein an induction time between        contacting of the monomer with the catalyst system, and the        onset of polymerization, is less than or equal to about 2        minutes for ethylene polymerization at about 100° C. to about        110° C., and about 450 psig to about 500 psig.    -   39A. The process of 37A-38A above, wherein the catalytic system        has an activity of greater than or equal to about 800 g/g/hr for        ethylene polymerization, wherein the ethylene polymerization is        conducted at about 100° C. to about 110° C., and about 450 psig        to about 500 psig.    -   40A. The process of 37A-39A above, wherein the monomer includes        C₂-C₆₀ olefins, C₂-C₂₀ alpha olefins, or a combination        comprising at least one of the foregoing.    -   41A. The process of 37A-40A above, carried out under slurry        phase polymerization conditions.    -   42A. The process of 37A-41A above, carried out under gas phase        polymerization conditions.    -   43A. The process of 37A-42A above, carried out under bulk phase        polymerization conditions.    -   44A. The process of 37A-43A above, wherein the catalyst        comprises a Group 6 metal.    -   45A. The process of 37A-44A above, wherein the catalyst        comprises chromium.    -   46A. The process of 37A-45A above, wherein the pores of the        support are arranged within the support such that a surface of        the pores define an inner surface of the support located        internal to an outer surface of the support, and wherein an        amount of the catalyst on the inner surface of the support is        greater than an amount of the catalyst on the outer surface of        the support, as determined by comparing the catalyst        concentration on essentially the surface of an amount of the        catalyst system, with the catalyst concentration of an amount of        the catalyst system which has been crushed.    -   47A. The process of 37A-46A above, wherein the support is        calcined at about 500° C. to about 750° C. for about 0.5 to        about 10 hours in air.    -   48A. The process of 37A-47A above, wherein greater than or equal        to about 80% of the pores have a pore diameter plus or minus        about 20% the average pore diameter.    -   49A. The process of 37A-48A above, wherein greater than or equal        to about 90% of the pores present have a pore diameter plus or        minus about 5% the average pore diameter.    -   50A. The process of 37A-49A above, wherein the average pore        diameter is about 20 Å to about 500 Å.    -   51A. The process of 37A-50A above, wherein the average pore        diameter is about 70 Å to about 90 Å.    -   52A. The process of 37A-51A above having a surface area greater        than or equal to about 300 m²/g support.    -   53A. The process of 37A-52A above, wherein the pore wall        thickness is less than or equal to about 20 Å.    -   54A. The process of 532A, wherein the pore wall thickness is        greater than or equal to about 4 Å.    -   55A. The process of 37A-54A above, wherein said crystalline        phase material has a composition expressed as follows:        M_(n/q)(W_(a)X_(b)Y_(c)Z_(d)O_(h))        where M is one or more ions; n is the charge excluding M        expressed as oxides;

-   q is the weighted molar average valence of M;

-   n/q is the number of moles or mole fraction of M;

-   W is one or more divalent elements;

-   X is one or more trivalent elements;

-   Y is one or more tetravalent elements;

-   Z is one or more pentavalent elements;

-   a, b, c, and d are mole fractions of W, X, Y, and Z, respectively;

-   h is a number of from 1 to 2.5; and

-   (a+b+c+d)=1.    -   56A. The process of 55A, wherein a and d are 0 and h=2.    -   57A. The process of 56A, wherein X comprises aluminum and Y        comprises silicon.    -   58A. The process of 57A, comprising about 0.1 to about 20 weight        percent alumina, based on the total weight of the support.    -   59A. The process of 37A-58A above having an average particle        size greater than or equal to about 1 micrometer.    -   60A. The process of 37A-59A above, comprising about 0.01 to        about 10 weight percent catalyst, based on the total weight of        the catalyst system.    -   61A. The polymer produced according to the process of 37A-60A        above, wherein the polymer comprises polyethylene.    -   62A. The polymer of 61A having a density of greater than or        equal to about 0.9 grams per cubic centimeter.    -   63A. A process to polymerize an unsaturated monomer, comprising:    -   contacting the monomer with a catalyst system of any of claims        of 16A to 33 A and optionally a scavenger, wherein the catalyst        system comprises a catalyst and a support comprising a        non-layered inorganic porous crystalline phase material calcined        at greater than or equal to about 200° C. for greater than or        equal to about 1 minute in the presence of an oxidizing gas,        wherein the support comprises a hexagonal arrangement of        uniformly-sized pores having an average pore diameter greater        than or equal to about 13 Å, an X-ray diffraction pattern having        a calculated d₁₀₀ value of greater than or equal to about 18A,        an adsorption capacity of greater than or equal to about 15        grams benzene per 100 grams support at 50 torr and at 25° C.,        and a pore wall thickness of less then or equal to about 25 Å.

While the invention has been described with reference to an exemplaryembodiment, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

1. A process to polymerize an olefin monomer, comprising: contacting themonomer with a catalyst system and optionally a scavenger, wherein thecatalyst system comprises an olefin polymerization catalyst and asupport comprising a non-layered inorganic porous crystalline phasematerial calcined at greater than or equal to about 200° C. for greaterthan or equal to about 1 minute in the presence of an oxidizing gas,wherein the support comprises a hexagonal arrangement of uniformly-sizedpores having an average pore diameter greater than or equal to about 13Å, an X-ray diffraction pattern having a calculated d₁₀₀ value ofgreater than or equal to about 18 Å, an adsorption capacity of greaterthan or equal to about 15 grams benzene per 100 grams support at 50 torrand at 25° C., and a pore wall thickness of less than or equal to about25 Å.
 2. The process of claim 1, wherein an induction time betweencontacting of the monomer with the catalyst system, and the onset ofpolymerization, is less than or equal to about 2 minutes for ethylenepolymerization at about 100° C. to about 110° C., and about 450 psig toabout 500 psig.
 3. The process of claim 1, wherein the catalytic systemhas an activity of greater than or equal to about 800 g/g/·hr forethylene polymerization, wherein the ethylene polymerization isconducted at about 100° C. to about 110° C., and about 450 psig to about500 psig.
 4. The process of claim 1, wherein the monomer includes C₂-C₆₀olefins, C₂-C₂₀ alpha olefins, or a combination comprising at least oneof the foregoing.
 5. The process of claim 1, carried out under slurryphase polymerization conditions.
 6. The process of claim 1, carried outunder gas phase polymerization conditions.
 7. The process of claim 1,carried out under bulk phase polymerization conditions.
 8. The processof claim 1, wherein the catalyst comprises a Group 6 metal.
 9. Theprocess of claim 1, wherein the catalyst comprises chromium.
 10. Theprocess of claim 1, wherein the pores of the support are arranged withinthe support such that a surface of the pores define an inner surface ofthe support located internal to an outer surface of the support, andwherein an amount of the catalyst on the inner surface of the support isgreater than an amount of the catalyst on the outer surface of thesupport, as determined by comparing the catalyst concentration onessentially the surface of the catalyst system with the catalystconcentration of the catalyst system which has been crushed.
 11. Theprocess of claim 1, wherein the support is calcined at about 500° C. toabout 750° C. for about 0.5 to about 10 hours in air.
 12. The process ofclaim 1, wherein greater than or equal to about 80% of the pores have apore diameter plus or minus about 20% the average pore diameter of thesupport.
 13. The process of claim 1, wherein greater than or equal toabout 90% of the pores present have a pore diameter plus or minus about5% the average pore diameter of the support.
 14. The process of claim 1,wherein the average pore diameter of the support is about 20 Å to about500 Å.
 15. The process of claim 1, wherein the average pore diameter ofthe support is about 70 Å to about 90 Å.
 16. The process of claim 1,having a surface area greater than or equal to about 300 m²/g support.17. The process of claim 1, wherein the pore wall thickness is less thanor equal to about 20 Å.
 18. The process of claim 16, wherein the porewall thickness is greater than or equal to about 4 Å.
 19. The process ofclaim 1, wherein said crystalline phase material has a compositionexpressed as follows:M_(n/q)(W_(a)X_(b)Y_(c)Z_(d)O_(h)) where M is one or more ions; n is thecharge excluding M expressed as oxides; q is the weighted molar averagevalence of M; n/q is the number of moles or mole fraction of M; W is oneor more divalent elements; X is one or more trivalent elements; Y is oneor more tetravalent elements; Z is one or more pentavalent elements; Ois oxygen; a, b, c, and d are mole fractions of W, X, Y, and Z,respectively; h is a number of from 1 to 2.5; and (a+b+c+d)=1.
 20. Theprocess of claim 19, wherein a and d are 0 and h=2.
 21. The process ofclaim 20, wherein X comprises aluminum and Y comprises silicon.
 22. Theprocess of claim 21, comprising about 0.1 to about 20 weight percentalumina, based on the total weight of the support.
 23. The process ofclaim 1 having an average particle size greater than or equal to about 1micrometer.
 24. The process of claim 1, comprising about 0.01 to about10 weight percent catalyst, based on the total weight of the catalystsystem.